Indigoid dyestuff



Patented July 31, 1928.

UNITED STATES 1,679,277 PATENT OFFICE.

HERMANN STAUDINGER, OF ZURICH, RICHARD TOBLER AND ROBERT STOCKER, OI

BASEL, J'AKOB M'U'LLER, 0F MUNCHENSTEIN, NEAR OF BASEL, SWITZERLAND, ASSIGNORS TO SOCIETY BASLE, or BASEL', SWITZERLAND.

.BASEL, AND ARMIN BUCHER, OF CHEMICAL INDUSTRY IN INDIGOID DYESTUFF.

No Drawing. Application filed November 24, 1923, Serial No. 676,858, and in Switzerland December 7, 1922.

The present invention relates to indigoid dyestuffs. It comprises the new dyestuffs, as well as the material dved with these dyestuffs.

It has been found that indigoid dyestuffs are obtained by reacting the compounds of the general formula:

(wherein C and C denote two carbon atoms 1 m 0:0 1, is

(wherein 2 denotes an exchangeable group, such as 0, two halides, one and, H and wherein m, 71/, and 1" denote atoms 01' residues of which two are carbon atoms adJa-cent to l g g.

i=0 i q} my each other, which at the same time belong to a ring of the benzene series, and of which the third atom may be NH or S).

As compounds of the general formula:

there may be mentioned the 1:2- and 2:3- thionaphthisatins, the 1 Q-and 2: 3- naphth thio-indoxyls, their halides and anils, as well as the halogen-substitution products of these .compounds.

As compounds of the general formula:

there may be mentioned quite commonly five-membered condensed ring systems, such as isatins, indoxyls,thioisatins, thioindoxyls,

and so forth, homologues and substitution products as well as halides and anils of these compounds.

The reactions which take place are illustrated by the following equations:

01 /O n+m E i) NH: a an N(CH:)

All of these new dyestuffs are characterized by the symmetrical grouping the first member of which is attached by the carbon atom C to the sulfur atom of a thionaphthol nucleus and by the carbon atom G to thesame thionaphthol by means of a Ll-carbon atom in ortho position to the sulfur atom, and in the second member of which C and C appertain to any five-membered condensed cyclic complex. The dyestuffs thus obtained may be further halogenated.

The shades and properties of some of the dyestuffs are given in the table hereinafter.

Example 1.

248.5 parts of e-chloro-l:Q-thionaphthisatin and 177 parts of indoxylcarboxylic acid are suspended in 5000 parts of alcohol and the mixture is heated for several hours to boiling. The mixture is then filtered and the dyestuif washed with alcohol and dried. It is a blue violet powder which dissolves in concentrated sulfuric acid to a green solution. It 'yields an olive-green vat which dyes cotton powerful blue violet tints which are very fast.

The new dyestufl' corresponds most probably with the following formula:

The same result is obtained if, instead of the 4-chloro-1:2-thionaphthisatin, there are employed the corresponding anils and chlorides, which compounds are of the same degree of oxidation as the isatin itself.

E wample 2.

The dyestulf yields a yel-' Eaample 3.-

214: parts of l:2-thionaphthisatin and 194 parts of oxythionaphthenecarhoxylic acid are suspended in 4000 parts of alcohol and the mixture is heated to boiling after addition of 5 parts of calcined sodium carbonate. A short boiling completes the condensation. The dyestull' separates in very good yield and is filtered, washed and dried. It is a brown red powder, which dissolves in sulfuric acid to a bright green solution. In its reddish-golden vat it dyes cotton Bordeaux red tints.

346 parts of this dyestull are added to 8000 parts of nitrobenzene and the mixture is mixed with 180 parts of bromine. In the course of a day the temperature is gradually raised to 180 C. during which operation a lively evolution of hydrogen bromide is to be observed. When the mixture is cooled the new product separates in the form of brown lustrous crystals. It dissolves in sulfuric acid to an intensely green solution and in its golden-yellow vat dyes cotton powerful and luminous Bordeaux tints which are very fast to soap.

The new dyestuif corresponds most probably with the following formula:

Mag i) l i E aample 4.

214 parts of 1:2-thionaphthisatin and 209 parts of G-aminothioindoxylcarboxylic acid are introduced into 7000 parts of alcohol and the mixture is boiled for some hours in a reflux apparatus. The condensation may be hastened by the addition of some ammonia or dimethylaniline. When condensation is complete the mixture is filtered and the dyestuff washed and dried. It forms a blackish-brown powder which dissolves in sulfuric acid of 98 per cent strength to a green blue solution. With hydrosullite and caustic soda solution it yields an orange brown vat which dyes wool and cotton fast brown tints. By brominating or benzoylating this dyestufl', for instance in the presence of pyridine, products of enhanced fastness to chloride are obtained.

E arample 5.

200 parts of 1:2-napththioindoxyl and 222 parts of a-lSillZlIl anilide are suspended in 4000 parts of alcohol and after addition of 5 parts of calcined sodium carbonate the mixture is heated to boiling; After boiling is continued for a short time the condensation is at an end. The dyestuFf which. separates in very good yield is filtered, washed and dried. It is a dark brown powder which dissolves in sulfuric acid to a green blue solution. It forms a greenyellow vat and dyes cotton violetgrey tintswhich become pure grey when soaped.

329 parts of this dyestuif are introduced, into 6000 parts of nitrobenzene and the whole is mixed with 176 parts of bromine. The mixture is allowed to after which its temperature is raised gradually to 120 C. during hours. The cooled mixture is filtered and the material on the filter is washed thoroughly with alcohol and dried. The new dyestuff is a violet powder which dissolves in sulfuric acid to a green blue solution. It dyes cotton from a golden yellow vat blueviolet tints which become a violet of good fastness when soaped.

rest for 24 hours,

reflux apparatus for some time. The dye stuff formed is filtered, washed and dried. The new (lyestufi' is a violet red powder, dissolves in concentrated sulfuric acid to an olive green solution and yields with hydrosulfite and caustic soda solution a yellow vat which dyes cotton red violet tints which are very fast to light, washing, boiling and chlorine.

The new dyestufi' corresponds most probably with the following formula:

Example 6.

248.5 parts of 1-chloro-2 3-thionaphthisa- The following table shows the main roptin and 194 parts of oxyth1onaphthenecarerties of some of the dyestuffs obtainab e acboxylic acid are introduced into 10,000 parts cording to this invention: of alcohol and the mixture 1s boiled in a Coupling component Coupling component 00101, Color in con- 0 l oentrated Color of vat 0 or or soaped 1 n nlsol dyeing I l: z-thionaphtbiaatin. Oxythionaphtheneearboxy- Brown red. Light green Reddish golden- Bordeaux red.

he sold. yellow. II Oxy'thlonaphthenecarboxy- Brown. Green. Gold yellow. Bordeaux red.

llc ac and brominating. III oamino-oxythionephthone. Black brown. Green blue. Orange brown. Brown. IV o-aminooxythlonaphthene Dark blue. Blue. Yellow brown. Brown.

and brominating. V I o-aniling-oxyilthtipnaphthene Black brown. Green blue. Orange brown. Brown. I an oy a ng. VI 4-cllill graiz lz2-thionaph- Indoxyl. Blue violet. Green. Olive green. Blue violet.

" Oxythiogaphthenecarbox- Red. Green. Yellow. Bordeaux red.

y 10 ac VIII 4-chloro--1:2-thi on ap'h- Oxythionaphthenwar b o x- Red. Green. Yellow. Bordeaux. thisatin. y ic acid and brominating.

IX 8-cnloro-1: 2-thionap h- Orythionaphthenecarb o r- Red. Green. Golden-yellow. Violet red.

thisatin. ylic acid;

" vOxythionaplitlienecarb o x- Red. Green. Golden-yellow. Violet.

ylic acid and brominating. XI 8-ch1oro-2:3-thionaph- G-chloro-oxythionaphthene- Dark brown. Green. Red yellow. Rcddish violet.

thisatin. cerboxylic acid. XII 2: 3-thionapbtl1isatin. fi-chlorooxivthionaphtheno- Blue grey. Green. Red orange. Violet.

carboxy c acid. XIII o-chloro-oxythionaphthene- Violet. Green. Red orange. Violet.

carboxylic acid and brominating. XIV pdimethylamln0anil ol Oxythionaphthene'. Blue grey. Green. Brown orange. Greenish grey. 2: 3-th'onaphthisatin. XV l-clfiljgggig! 3-thionaphoxy thiog aphthenecarbox- Violet red. Olive green. Yellow. Red violet.

t y c ac XVI Oxythionaphthenecarbox- Violet red. Olive green. Yellow. Red violet.

ylic acid and brominating. XVII Indoxyl. Reddiah blue. Blue. Orange yellow. Violet. XVIII O-chlorooxythionaphthene. Violet red. Olive green range. Red vio et. XIX 5-ctllilligo lz2-thionaphoxyithioiziiiaphthenecarbox- Red brown. Green. Golden yellow. Bordeaux.

m i y 0 ac XX 7 Oxythionaphthenecarbox- Dark violet. Green. Golden yellow. Bordeaux.

ylic acid and brominating. XXI lzz-nephththioindoxyL- 5:7-dibror'noisatin. Brown. Violet red. Yellow. Brown, XXII 5z7 iibromoleatin chloride. Violet. Blue. Golden yellow. Blue violet. XXIII A-chlpro-hZ-naphththio- 5:7-dibromoieatin. Red. Violet red. Yellow. Brown.

in or XXIV 2(t4h'id lmtethylamlno)-anil of Blue red. Green. Yellow. Bordeaux.

else in. XXV a-isetln anilide. Violet blue. Reddish blue. 1 Orange brown. Heliotrope. XXVI a-isattiin anilide and bromi- Violet blue. Greeniah blue. Orange brown. Violet.

no on. XXVII 4chloro-1z2-naphththio- 6:7-dibromoleatin chloride. Violet. Greenish blue. Yellow red. Violet.

in ex 1 XXVII I 8ri:hlpro-2z3-naphththio- Dibrornoioatln. Reddish violet Deep green. Golden yellow. Violet.

n or XXIX 2: 3-naphththioindoxyl. 5:7-dibromoiaatin. Reddish violet. Violet. Golden yellow. Violet, XXX 1 pfiethylamlno-thloisatin- Bluish grey. Green. Brown orange. Greenish grey. XXXI *pdimethylamino-thioisatin- Reddish violet. Olive green. Brown orange. Reddish violet.

nail and bromination. XXXII l-chlpro-zlzti-naphththio- 5:7-dibromoiaatln chloride. Violet. Green. Brown orange. Blue.

In oxy The formula of dyestuff III is most probably:

The formula of dyestufi' No. V is most probably the following:

s Nnoocm The formula of dyestuff X is most probably:

@i if) m The formula of dyes ntf XI is most probably:

The formula of dyestufi' XXVI is most probably:

NH s--o=o d \C ll The formula of dyestull XXVTII is most probably:

Br c=c 1 1K ll a The formula of dyestutl' XXXII is most probably:

the first member of which is attached by the carbon atom C to the sulfur atom of a thionaphthol nucleus and by the carbon atom C to a ,8-C-atom in ortho-position to this sulfur atom, and the second member of which belongs to a live lnembered hetcrocyclic complex containing a S-atom or a Nll-group and condensed with a benzene nucleus which dyestuffs form dark powders which dissolve in sulfuric acid of 98 per cent strength with violet-red to green and olive color, yielding with hydrosulfite and caustic soda solution yellow to olive-green vats which dye cotton fast brown to Bordeaux, violet, blue and gray tints.

2. As new products the unsymmetrical indigoid dyestuffs which are characterized by the atom grouping ll ll the first member of which is attached by the carbon atom C to the sulfur atom of a halogenated thionaphthol nucleus and by the carbon atom C to a ,B-C-atom in ortho-position to this sulfur atom, and in which R stands for S and NH and wherein the henzene nucleus may carry substituents, which dyestuffs form dark powders which dissolve in sulfuric acid of 98 per cent strength with reddish-blue to green and olive color, yielding with hydrosulfite and caustic soda solution yellow to olive-green vats which dye ill) ' 'hydrosulfite and caustic soda carry substituents,

' 'color, yielding with hydrosu'lfite and cotton fast brown and gray tints.

3. As new products the unsymmetrical indigoid dyestuffs which are characterized by the atom grouping wherein the naphthalene nucleus is halogenized, R standing for NH or S and in which the benzene nucleus may carry substituents, which dyestufis form red-violet to brownblack and green-blue powders which dissolve in concentrated sulfuric acid with red-violet to blue and olive green color, yielding with solution yellow to orange and brown vats which dye cotton fast red-violet to green-blue tints. 4. As new products the unsymmetrical indigoid dyestufi's which are characterized by the atom grouping wherein the naphthalene nucleus is halogenized and in which the benzene nucleus may which dyestufi's' form violet to brown owders which dissolve in concentrated sul uric acid with olive-green caustic sodatsolution yellow to oran e and brownorange vats which dye cotton ast violet tints.

to Bordeaux, violet, blue 5. Materials dyed with the dyestuffs of claim 1.

6. Materials dyed with the dyestuifs of claim 2.

7. Materials dyed with the dyestufl's of claim 3.

8. Materials yed with the dyestufi's of claim 4.

9. 'As new products the asymmetrical, sulfur containing vat dyestuffs of the formula wherein'X re resents hydrogen or alkyl and Y represents ydrogenor-halogen, and H1, stands for a halogen having an atomic weight between and 80, and the arrow indicates that the position of the halogen in the naphthalene nucleus is undetermined; which dyestufis are violet powders dissolving in hot concentrated sulfuric acid, with a green coloration, insoluble in water, dilute acids or alkalies, and dye textile fibers from the vat violet shades;

In witness whereof we have hereunto signed our names this 3rd day of November 1923.

HERMANN STAUDINGER. RICHARD TOBLER. ROBERT s rooKER, JAKOB MULLER.

ARMIN BUCHER. 

